CN-117000240-B - Trimetallic active carbon supported catalyst and application thereof

CN117000240BCN 117000240 BCN117000240 BCN 117000240BCN-117000240-B

Abstract

The invention discloses a trimetallic active carbon supported catalyst and application thereof, wherein active carbon is used as a carrier, and a first metal element, a second metal element and an auxiliary metal element are supported on the carrier, wherein the first metal element is selected from Rh, W and Ir, the second metal element is selected from Ga, sn and Mg, and the auxiliary metal element is selected from La, ce and Y. The method is applied to the preparation of 4-heptanol by catalytic hydrogenation of 4-heptanone, the product selectivity of the 4-heptanol can reach 100% when the conversion rate of the 4-heptanone reaches 100%, the separation and purification burden of the later-stage product can be greatly reduced, the production cost is reduced, the solvent is not used in the catalytic reaction process, the reaction temperature is low, the green production requirement is met, the catalyst has high activity, the reaction time is short, and the production efficiency can be improved.

Inventors

YANG ZHAO
LIU YU
LI TING
YU YONGQI

Assignees

南阳师范学院

Dates

Publication Date: 20260505
Application Date: 20230727

Claims (4)

1. The application of the trimetallic active carbon supported catalyst in preparing 4-heptanol by 4-heptanone hydrogenation is characterized in that an intermittent autoclave liquid phase hydrogenation process is adopted, no solvent is used, in the intermittent autoclave liquid phase hydrogenation process, the hydrogen pressure is 0.5-5.5MPa, the reaction temperature is 20-50 ℃, the catalyst feeding amount/substrate is 0.001-0.01g/mL, and the reaction time is 0.5-2h; the three-metal active carbon supported catalyst takes active carbon as a carrier, and is loaded with a first metal element, a second metal element and an auxiliary metal element, wherein the first metal element is selected from Rh, W and Ir, the second metal element is selected from Ga, sn and Mg, the auxiliary metal element is selected from La, ce and Y, the loading capacity of the first metal element is 0.1-1.6 wt percent, the loading capacity of the second metal element is 0.5-1.6 wt percent, and the loading capacity of the auxiliary metal element is 0.1-1.5 wt percent; The preparation process of the trimetallic active carbon supported catalyst comprises the steps of firstly supporting auxiliary metal elements on active carbon, then simultaneously supporting a first metal element and a second metal element on the active carbon, adopting salt solution of a metal precursor to be mixed with the active carbon, soaking and stirring, adding a surfactant, regulating the pH value to 0.5-5.5 or 8-13, adding a chemical reducing agent for reduction, filtering and washing to be neutral, and then vacuum drying at 75-85 ℃ for 10-12h; The three-metal active carbon supported catalyst needs to be pretreated by hydrogen-nitrogen mixed gas before feeding, wherein the pretreatment is carried out by the hydrogen-nitrogen mixed gas through a catalyst bed layer, the gas flow is 40-80 mL/min, the hydrogen content in the hydrogen-nitrogen mixed gas is 4-6%, the pretreatment temperature is 200-500 ℃, the heating rate is 2-10 ℃ per min, and the pretreatment time is 1-6h.
2. A method for preparing 4-heptanol by 4-heptanone hydrogenation is characterized in that a trimetallic activated carbon supported catalyst is adopted, and the trimetallic activated carbon supported catalyst is subjected to pretreatment of hydrogen-nitrogen mixed gas before feeding, wherein the pretreatment is carried out by a catalyst bed layer, the gas flow is 40-80 mL/min, the hydrogen content in the hydrogen-nitrogen mixed gas is 4-6%, the pretreatment temperature is 200-500 ℃, the heating rate is 2-10 ℃ per min, and the pretreatment time is 1-6h; the three-metal active carbon supported catalyst takes active carbon as a carrier, and is loaded with a first metal element, a second metal element and an auxiliary metal element, wherein the first metal element is selected from Rh, W and Ir, the second metal element is selected from Ga, sn and Mg, the auxiliary metal element is selected from La, ce and Y, the loading capacity of the first metal element is 0.1-1.6 wt percent, the loading capacity of the second metal element is 0.5-1.6 wt percent, and the loading capacity of the auxiliary metal element is 0.1-1.5 wt percent; The preparation process of the trimetallic active carbon supported catalyst comprises the steps of firstly supporting auxiliary metal elements on active carbon, then simultaneously supporting first metal elements and second metal elements on the active carbon, adopting salt solution of metal precursors to mix with the active carbon, soaking and stirring, adding surfactant, regulating pH to 0.5-5.5 or 8-13, adding chemical reducing agent for reduction, filtering and washing to neutrality, and then vacuum drying at 75-85 ℃ for 10-12h.
3. The method of claim 2, wherein the batch autoclave liquid phase hydrogenation process is conducted without the use of a solvent.
4. The method of claim 3, wherein the hydrogen pressure is 0.5-5.5MPa, the reaction temperature is 20-50 ℃, the catalyst dosage/substrate is 0.001-0.01g/mL, and the reaction time is 0.5-2h.

Description

Trimetallic active carbon supported catalyst and application thereof Technical Field The invention belongs to the technical field of industrial catalysts, and particularly relates to a trimetallic activated carbon supported catalyst and application thereof. Background The 4-heptanol is an important chemical raw material, can be used as an upstream raw material for fine organic synthesis, and belongs to an important medical intermediate and a material intermediate. The 4-heptanol can be prepared by hydrogenating 4-heptanone, and no related catalyst patent for preparing the 4-heptanol by hydrogenating the 4-heptanone is known at present. The prior art discloses catalysts and processes for preparing alcohols by hydrogenating ketones. CN1152744C, CN1114490C and CN1347758A disclose a process for preparing sec-octanol by hydrogenating sec-octanone, which is realized by using a self-made catalyst system (copper-containing catalyst and nickel-containing catalyst) and adopting a fixed bed liquid phase hydrogenation process, wherein the reaction temperature is 100-250 ℃. The selectivity of the secondary octanol is 96-99.5%. CN1974514A discloses a method for preparing 2-octanol by hydrogenation reduction of 2-octanone, which comprises the steps of adding a hydrogenation catalyst with ferromagnetism into a magnetically stabilized bed reactor, and reacting at 70-120 ℃ under the conditions that the pressure is 0.3-2.5MPa, the liquid volume space velocity is 1-50h < -1 >, the volume ratio of hydrogen to a solution containing 2-octanone is 2-100:1, and the magnetic field strength is 10-50kA/m, wherein the yield of 2-octanol can reach 70%. Patent CN1083415C adopts a CuO-ZnO mixture formed by tabletting as a catalyst, and the conversion rate and the selectivity of the isopropanol prepared by the vapor phase hydrogenation of the acetone reach 99 percent under the condition of the reaction temperature of 150-250 ℃. The Ru/Al2O3 catalytic acetone hydrogenation technology disclosed in Japanese patent application No. 2-279643 is harsh, the reaction pressure is 9MPa, and the investment of equipment is large. Japanese patent publication No. Hei-41038, soviet Union patent SU1118632A describes an acetone hydrogenation method using a Cu-Cr catalyst, russian patent RU2047590 uses a catalyst containing components such as NiO, cuO and the like, but the conversion rate of the catalyst is not high, the selectivity is poor, and the use of Cr2O3 as an auxiliary agent causes environmental pollution and does not meet the requirements of green chemical industry. CN103030525A discloses a method for preparing isopropanol by liquid phase hydrogenation of acetone, but the reaction temperature is higher, the conversion rate of acetone is more than 96% at 100-200 ℃, and the selectivity of isopropanol is more than 95%. CN1962588 discloses that a catalyst loaded on activated carbon by nickel-cobalt bimetallic is used for continuous gas-phase hydrogenation reaction of acetone, the reaction temperature is 100-150 ℃, the pressure is 1.0-1.5MPa, and higher acetone conversion rate and isopropanol selectivity can be obtained. CN103706365 discloses that the nickel-copper bimetallic supported catalyst is used for the hydrogenation of acetone by a normal pressure gas phase fixed bed, the reaction temperature is 100-150 ℃, the selectivity of isopropanol reaches 100%, and the conversion rate of acetone can reach more than 85.5%. CN103706377a, CN103752327a discloses the preparation of isopropanol by liquid phase hydrogenation of acetone with metal catalysts of Pt, fe, sn, co as main components, the reaction temperature is 100-150 ℃ and the reaction time is 4h. USP4,182,721 discloses a molybdenum modified skeletal nickel catalyst for catalytic hydrogenation of ketones, which has poor selectivity in spite of mild reaction conditions (60 ℃ C., 2.1 MPa). USP4,459,419 discloses a process for hydrogenating organic ketones or aldehydes using a ruthenium catalyst supported on a molecular sieve and exemplifies the use of furfuryl alcohol hydrogenation to tetrahydrofurfuryl alcohol, but the pressure required for the reaction system is relatively high, up to 12.7MPa. The operation temperature of the catalytic hydrogenation reaction of the ketone compounds disclosed in the prior art is high, or the operation condition has high requirements on equipment, or the conversion rate and the selectivity of the products can not reach high standards at the same time. Therefore, if a heterogeneous catalyst which can react at a lower operating temperature without using a solvent and has high activity and high product selectivity is developed, the burden of a product separation and purification link can be reduced, the energy consumption can be reduced, and the cost of the production process can be greatly reduced. The production meets the production requirements of green chemical industry with low energy consumption and high efficiency. Disclosure of Invention The invention aims to